U.S. patent number 10,723,841 [Application Number 16/047,674] was granted by the patent office on 2020-07-28 for method for preparing compound and method for preparing polymer employing the same.
This patent grant is currently assigned to INDUSTRIAL TECHNOLOGY RESEARCH. The grantee listed for this patent is INDUSTRIAL TECHNOLOGY RESEARCH INSTITUTE. Invention is credited to Yih-Her Chang, Chien-Ming Chen, Cheng-Hsing Fan, Po-Hsien Ho, Hsin-Ching Kao, Chih-Hsiang Lin, Feng-Jen Tsai.
View All Diagrams
United States Patent |
10,723,841 |
Ho , et al. |
July 28, 2020 |
Method for preparing compound and method for preparing polymer
employing the same
Abstract
A method for preparing a compound and a method for preparing a
polymer employing the same are provided. The method for preparing a
compound includes reacting a compound having a structure
represented by Formula (I) with a compound having a structure
represented by Formula (III) in the presence of a compound having a
structure represented by Formula (II) to obtain a compound having a
structure represented by Formula (IV) ##STR00001## wherein Ar.sup.1
is substituted or unsubstituted aryl group; X is --O--, --S--, or
--NH--; R.sup.1 is independently hydrogen or C.sub.1-6 alkyl group;
R.sup.2 is hydroxyl group, C.sub.1-6 alkyl group, phenyl group, or
tolyl group; and R.sup.3 is independently C.sub.1-6 alkyl group,
C.sub.5-8 cycloalkyl group, or C.sub.2-6 alkoxyalkyl group.
Inventors: |
Ho; Po-Hsien (Taipei,
TW), Lin; Chih-Hsiang (Taipei, TW), Tsai;
Feng-Jen (Taipei, TW), Fan; Cheng-Hsing (Tainan,
TW), Chang; Yih-Her (Baoshan Township, TW),
Kao; Hsin-Ching (Baoshan Township, TW), Chen;
Chien-Ming (Taoyuan, TW) |
Applicant: |
Name |
City |
State |
Country |
Type |
INDUSTRIAL TECHNOLOGY RESEARCH INSTITUTE |
Hsinchu |
N/A |
TW |
|
|
Assignee: |
INDUSTRIAL TECHNOLOGY RESEARCH
(Hsinchu, TW)
|
Family
ID: |
63244384 |
Appl.
No.: |
16/047,674 |
Filed: |
July 27, 2018 |
Prior Publication Data
|
|
|
|
Document
Identifier |
Publication Date |
|
US 20190040202 A1 |
Feb 7, 2019 |
|
Related U.S. Patent Documents
|
|
|
|
|
|
|
Application
Number |
Filing Date |
Patent Number |
Issue Date |
|
|
62539681 |
Aug 1, 2017 |
|
|
|
|
Foreign Application Priority Data
|
|
|
|
|
Dec 27, 2017 [TW] |
|
|
106145978 A |
|
Current U.S.
Class: |
1/1 |
Current CPC
Class: |
C08G
75/02 (20130101); C08G 75/029 (20130101); C08G
75/20 (20130101); C07C 319/20 (20130101); C07C
319/14 (20130101); C07C 315/02 (20130101); C08G
75/23 (20130101); C08G 75/0272 (20130101); C07C
315/00 (20130101); C07C 317/22 (20130101); C07C
323/00 (20130101); C08G 75/0227 (20130101); C08G
75/0236 (20130101); C08G 75/025 (20130101); C07C
319/20 (20130101); C07C 321/30 (20130101); C07C
319/14 (20130101); C07C 323/20 (20130101); C07C
315/02 (20130101); C07C 317/22 (20130101) |
Current International
Class: |
C08G
75/0236 (20160101); C08G 75/02 (20160101); C08G
75/23 (20060101); C08G 75/029 (20160101); C08G
75/0227 (20160101); C07C 315/02 (20060101); C07C
319/14 (20060101); C08G 75/025 (20160101); C08G
75/20 (20160101); C07C 323/00 (20060101); C07C
317/22 (20060101); C07C 319/20 (20060101); C07C
315/00 (20060101) |
References Cited
[Referenced By]
U.S. Patent Documents
Foreign Patent Documents
|
|
|
|
|
|
|
101033294 |
|
Sep 2007 |
|
CN |
|
101092479 |
|
Dec 2007 |
|
CN |
|
101774953 |
|
Jul 2010 |
|
CN |
|
102516139 |
|
Jun 2012 |
|
CN |
|
105492498 |
|
Apr 2016 |
|
CN |
|
3190139 |
|
Jul 2017 |
|
EP |
|
3190140 |
|
Jul 2017 |
|
EP |
|
3190141 |
|
Jul 2017 |
|
EP |
|
3190142 |
|
Jul 2017 |
|
EP |
|
3190143 |
|
Jul 2017 |
|
EP |
|
7-304872 |
|
Nov 1995 |
|
JP |
|
8-245558 |
|
Sep 1996 |
|
JP |
|
2016-147955 |
|
Aug 2016 |
|
JP |
|
2017-125014 |
|
Jul 2017 |
|
JP |
|
2017-125190 |
|
Jul 2017 |
|
JP |
|
2017-160185 |
|
Sep 2017 |
|
JP |
|
2017-197712 |
|
Nov 2017 |
|
JP |
|
2017-197713 |
|
Nov 2017 |
|
JP |
|
201512249 |
|
Apr 2015 |
|
TW |
|
Other References
Dizman, C., et al, "Recent advances in the preparation of
functionalized polysulfones," Polymer International, 2013, vol. 62,
p. 991-1007. cited by applicant .
Matsumoto, K., et al, "Synthesis of poly(ether sulfone)s by
self-polycondensation of AB-type monomers," Polymer Journal, 2013,
vol. 45, pp. 909-914. cited by applicant .
Tsuchida, E., et al, "Synthesis of High Molecular Weight
Poly(phenylene sulfide) by Oxidative Polymerization via
Poly(sulfonium cation) from Methyl Phenyl Sulfoxide,"
Macromolecules, 1993, vol. 26, pp. 7144-7148. cited by applicant
.
Tsuchida, E., et al, "Synthetic Route to
Poly(sulfonyl-1,4-phenylenethio-1,4-phenylene) via a Poly(sulfonium
cation)," Macromolecules, 1993. vol. 26, pp. 7389-7390. cited by
applicant .
Yokozawa, T., et al, "Chain-growth polycondensation: The living
polymerization process in polycondensation," Progress in Polymer
Science, Jan. 1, 2007, vol. 32, pp. 147-172. cited by applicant
.
Taiwanese Notice of Allowance and Search Report, dated Dec. 25,
2018, for Taiwanese Application No. 106145978. cited by applicant
.
Cogolli et al., "Nucleophilic Aromatic Substitution Reactions of
Unactivated Aryl Halides With Thiolate Ions in
Hexamethylphosphoramide", The Journal of Organic Chemistry, vol.
44, No. 15, Jul. 1, 1979, pp. 2642-2646. cited by applicant .
Ding et al., "Preparation of Poly(thioarylene)s From Cyclic
Disulfide Oligomers", Macromolecules, American Chemical Society,
vol. 30, No. 9, May 5, 1997 (abstract published Apr. 1997), pp.
2527-2531. cited by applicant .
Extended European Search Report dated Jan. 4, 2019, for
corresponding European Application No. 18186311.9. cited by
applicant .
Gabler et al., "Neue Polyphenylensulfone Reaktionen An Festen
Polymeren", Chimia International Journal for Chemistry, vol. 28,
No. 9. Sep. 1974, pp. 567-575. cited by applicant .
Miller et al., "Reactions of Diaryl Disulfides with Active,
Nonnucleophilic Alkylating Agents", Journal of Organic Chemistry,
vol. 36, No. 11, Jun. 1, 1971, pp. 1513-1519. cited by applicant
.
Tsuchida et al., "Polymerization at Diphenyl Disulfide by the S--S
Bond Cleavage With a Lewis Acid: A Novel Preparation Route to
Poly(p-phenylene sulfide)", Macromolecules, vol. 23, No. 8, Apr.
16, 1990 pp. 2101-2106. cited by applicant .
Japanese Office Action dated Jun. 25, 2019, for corresponding
Japanese Application No. 2018-142980, with English translation.
cited by applicant .
Jilek et al., "Potential metabolites of the neuroleptic agents
belonging to the
8-(methylthio)-10-piperazino-10,11-dihydrodibenzo[b,f]thiepin
series; Synthesis of 2-hydroxy and 3-hydroxy derivatives",
Collection Czechoslovak Chem. Commun., vol. 50, 1985, pp.
2179-2190. cited by applicant.
|
Primary Examiner: Fang; Shane
Attorney, Agent or Firm: Birch, Stewart, Kolasch &
Birch, LLP
Parent Case Text
CROSS REFERENCE TO RELATED APPLICATIONS
This application claims the benefit of U.S. Provisional Application
No. 62/539,681, filed on Aug. 1, 2017, which is hereby incorporated
by reference herein.
The application is based on, and claims priority from, Taiwan
Application Serial Number 106145978, filed on Dec. 27, 2017, the
disclosure of which is hereby incorporated by reference herein in
its entirety.
Claims
What is claimed is:
1. A method for preparing a compound, comprising: reacting a
compound having a structure represented by Formula (I) with a
compound having a structure represented by Formula (III) in the
presence of a compound having a structure represented by Formula
(II), obtaining a compound having a structure represented by
Formula (IV) ##STR00047## wherein Ar.sup.1 is substituted or
unsubstituted aryl group; X is --O--, --S--, or --NH--; R.sup.1 is
independently hydrogen or C.sub.1-6 alkyl group; R.sup.2 is
hydroxyl group, C.sub.1-6 alkyl group, phenyl group, or tolyl
group; and R.sup.3 is independently C.sub.1-6 alkyl group,
C.sub.5-8 cycloalkyl group, or C.sub.2-6 alkoxyalkyl group.
2. The method as claimed in claim 1, wherein Ar.sup.1 is
substituted or unsubstituted phenyl group, biphenyl group, naphthyl
group, thienyl group, indolyl group, phenanthrenyl group, indenyl
group, anthracenyl group, or fluorenylene group.
3. The method as claimed in claim 1, wherein R.sup.1 is
independently hydrogen, methyl group, ethyl group, propyl group,
isopropyl group, n-butyl group, t-butyl group, sec-butyl group,
isobutyl group, pentyl group, or hexyl group.
4. The method as claimed in claim 1, wherein the compound having
the structure of Formula (I) is ##STR00048## wherein R.sup.1 is
independently hydrogen or C.sub.1-6 alkyl group; and R.sup.4 is
independently hydrogen or C.sub.1-6 alkyl group.
5. The method as claimed in claim 1, wherein the compound having
the structure of Formula (II) is sulfuric acid, methanesulfonic
acid, benzenesulfonic acid, p-toluenesulfonic acid, or a
combination thereof.
6. The method f as claimed in claim 1, wherein R.sup.3 is
independently methyl group, ethyl group, propyl group, isopropyl
group, n-butyl group, t-butyl group, sec-butyl group, isobutyl
group, pentyl group, hexyl group, cyclopentyl group, cyclohexyl
group, cycloheptyl group, cyclooctyl group, or ##STR00049## wherein
1.ltoreq.n.ltoreq.5, 0.ltoreq.m.ltoreq.4, and
1.ltoreq.n+m.ltoreq.5.
7. The method as claimed in claim 1, wherein the compound having
the structure of Formula (IV) is ##STR00050## ##STR00051## wherein
R.sup.1 is independently hydrogen or C.sub.1-6 alkyl group; R.sup.4
is independently hydrogen or C.sub.1-6 alkyl group; and R.sup.3 is
independently C.sub.1-6 alkyl group, C.sub.5-8 cycloalkyl group, or
C.sub.2-6 alkoxyalkyl group.
8. The method as claimed in claim 1, further comprising: reacting
the compound having the structure represented by Formula (IV) with
a compound (A), obtaining a compound having the structure
represented by Formula (V) ##STR00052## wherein the compound (A) is
nitric acid, sulfuric acid, acetic acid, hydrogen peroxide, or a
combination thereof; Ar.sup.1 is substituted or unsubstituted; X is
--O--, --S--, or --NH--; R.sup.1 is independently hydrogen or
C.sub.1-6 alkyl group; and R.sup.3 is independently C.sub.1-6 alkyl
group, C.sub.5-8 cycloalkyl group, or C.sub.2-6 alkoxyalkyl
group.
9. The method as claimed in claim 8, wherein the compound having
the structure of Formula (V) is ##STR00053## ##STR00054## wherein
R.sup.1 is independently hydrogen or C.sub.1-6 alkyl group; R.sup.4
is independently hydrogen or C.sub.1-6 alkyl group; and R.sup.3 is
independently C.sub.1-6 alkyl group, C.sub.5-8 cycloalkyl group, or
C.sub.2-6 alkoxyalkyl group.
10. A method for preparing a polymer, comprising: reacting a
compound having a structure represented by Formula (I) with a
compound having a structure represented by Formula (III) in the
presence of a compound having a structure represented by Formula
(II), obtaining a compound having a structure represented by
Formula (IV); reacting the compound having the structure
represented by Formula (IV) with a compound (A), obtaining a
compound having the structure represented by Formula (V), wherein
the compound (A) is nitric acid, sulfuric acid, acetic acid,
hydrogen peroxide, or a combination thereof; and reacting the
compound having the structure represented by Formula (V) with a
compound having a structure represented by Formula (VI), obtaining
a polymer having a repeat unit represented by Formula (VII)
##STR00055## wherein Ar.sup.1 is substituted or unsubstituted aryl
group; X is --O--, --S--, or --NH--; R.sup.1 is independently
hydrogen or C.sub.1-6 alkyl group; R.sup.2 is hydroxyl group,
C.sub.1-6 alkyl group, phenyl group, or tolyl group; R.sup.3 is
independently C.sub.1-6 alkyl group, C.sub.5-8 cycloalkyl group, or
C.sub.2-6 alkoxyalkyl group; R.sup.5 is hydroxyl group, C.sub.1-6
alkyl group, phenyl group, or tolyl group; and Ar.sup.2 is
substituted or unsubstituted aryl diradical.
11. The method as claimed in claim 10, wherein Ar.sup.1 is
substituted or unsubstituted phenyl group, biphenyl group, naphthyl
group, thienyl group, indolyl group, phenanthrenyl group, indenyl
group, anthracenyl group, or fluorenylene group.
12. The method as claimed in claim 10, wherein R.sup.1 is
independently hydrogen, methyl group, ethyl group, propyl group,
isopropyl group, n-butyl group, t-butyl group, sec-butyl group,
isobutyl group, pentyl group, or hexyl group.
13. The method as claimed in claim 10, wherein the compound having
the structure of Formula (I) is ##STR00056## ##STR00057## wherein
R.sup.1 is independently hydrogen or C.sub.1-6 alkyl group; and
R.sup.4 is independently hydrogen or C.sub.1-6 alkyl group.
14. The method as claimed in claim 10, wherein the compound having
the structure of Formula (II) is sulfuric acid, methanesulfonic
acid, benzenesulfonic acid, p-toluenesulfonic acid or a combination
thereof.
15. The method as claimed in claim 10, wherein R.sup.3 is
independently methyl group, ethyl group, propyl group, isopropyl
group, n-butyl group, t-butyl group, sec-butyl group, isobutyl
group, pentyl group, hexyl group, cyclopentyl group, cyclohexyl
group, cycloheptyl group, cyclooctyl group, or ##STR00058## wherein
1.ltoreq.n.ltoreq.5, 0.ltoreq.m.ltoreq.4, and
1.ltoreq.n+m.ltoreq.5.
16. The method as claimed in claim 10, wherein the compound having
the structure of Formula (IV) is ##STR00059## ##STR00060## wherein
R.sup.1 is independently hydrogen or C.sub.1-6 alkyl group; R.sup.4
is independently hydrogen or C.sub.1-6 alkyl group; and R.sup.3 is
independently C.sub.1-6 alkyl group, C.sub.5-8 cycloalkyl group, or
C.sub.2-6 alkoxyalkyl group.
17. The method as claimed in claim 10, wherein the compound having
the structure of Formula (V) is ##STR00061## ##STR00062## wherein
R.sup.1 is independently hydrogen or C.sub.1-6 alkyl group; R.sup.4
is independently hydrogen or C.sub.1-6 alkyl group; and R.sup.3 is
independently C.sub.1-6 alkyl group, C.sub.5-8 cycloalkyl group, or
C.sub.2-6 alkoxyalkyl group.
18. The method as claimed in claim 10, wherein the compound having
the structure of Formula (VI) is sulfuric acid, methanesulfonic
acid, benzenesulfonic acid, p-toluenesulfonic acid, or a
combination thereof.
19. The method as claimed in claim 10, wherein Ar.sup.2 is
substituted or unsubstituted phenylene group, biphenylene group,
naphthylene group, thienylene group, indolylene group,
phenanthrenylene group, indenylene group, anthracenylene group, or
fluorenylene group.
20. The method as claimed in claim 10, further comprising: reacting
a nucleophile with the polymer having the repeat unit represented
by Formula (VII), obtaining a polymer having a repeat unit
represented by Formula (VIII) ##STR00063## wherein X is --O--,
--S--, or --NH--; R.sup.1 is independently hydrogen or C.sub.1-6
alkyl group; R.sup.3 is independently C.sub.1-6 alkyl group,
C.sub.5-8 cycloalkyl group, or C.sub.2-6 alkoxyalkyl group; R.sup.5
is hydroxyl group, C.sub.1-6 alkyl group, phenyl group, or tolyl
group; and Ar.sup.2 is substituted or unsubstituted aryl
diradical.
21. The method as claimed in claim 20, wherein the nucleophile is
pyridine, 4-methylpyridine, triethylamine, potassium chloride,
methanol, ethanol, dimethylformamide, dimethylacetamide,
N-methylpyrrolidone, or a combination thereof.
22. The method as claimed in claim 20, when X of the polymer having
the repeat unit represented by Formula (VIII) is --O-- or --NH--,
further comprising: reacting the polymer having the repeat unit
represented by Formula (VIII) with hydrogen peroxide, obtaining a
polymer having a repeat unit represented by Formula (X)
##STR00064## wherein X is --O-- or --NH--; R.sup.1 is independently
hydrogen or C.sub.1-6 alkyl group; and Ar.sup.2 is substituted or
unsubstituted aryl diradical.
23. The method as claimed in claim 20, wherein a polymer having the
repeat unit represented by Formula (VIII) is reacted with hydrogen
peroxide in the presence of a compound having a structure
represented by Formula (IX) ##STR00065## wherein R.sup.6 is
C.sub.1-6 alkyl group.
24. The method as claimed in claim 10, when X of the polymer having
the repeat unit represented by Formula (VII) is --S--, further
comprising: reacting the polymer having the repeat unit represented
by Formula (VII) with hydrogen peroxide, obtaining a polymer having
a repeat unit represented by Formula (XI) ##STR00066## wherein X is
--S--; R.sup.1 is independently hydrogen or C.sub.1-6 alkyl group;
R.sup.3 is independently C.sub.1-6 alkyl group, C.sub.5-8
cycloalkyl group, or C.sub.2-6 alkoxyalkyl group; R.sup.5 is
hydroxyl group, C.sub.1-6 alkyl group, phenyl group, or tolyl
group; and Ar.sup.2 is substituted or unsubstituted aryl
diradical.
25. The method as claimed in claim 24, wherein the polymer having
the repeat unit represented by Formula (VII) is reacted with
hydrogen peroxide in the presence of a compound having a structure
represented by Formula (IX) ##STR00067## wherein R.sup.6 is
C.sub.1-6 alkyl group.
26. The method as claimed in claim 24 further comprising: reacting
a nucleophile with the polymer having the repeat unit represented
by Formula (XI), obtaining a polymer having a repeat unit
represented by Formula (XII) ##STR00068## wherein R.sup.1 is
independently hydrogen or C.sub.1-6 alkyl group; R.sup.3 is
independently C.sub.1-6 alkyl group, C.sub.5-8 cycloalkyl group, or
C.sub.2-6 alkoxyalkyl group; R.sup.5 is hydroxyl group, C.sub.1-6
alkyl group, phenyl group, or tolyl group; and Ar.sup.2 is
substituted or unsubstituted aryl diradical.
27. The method as claimed in claim 26, wherein the nucleophile is
pyridine, 4-methylpyridine, triethylamine, potassium chloride,
methanol, ethanol, dimethylformamide, dimethylacetamide,
N-methylpyrrolidone, or a combination thereof.
Description
TECHNICAL FIELD
The technical field relates to a method for preparing a compound
and a method for preparing a polymer.
BACKGROUND
Polyarylene sulfide (PAS) (or polythioether sulfone (PTES)) is a
material with good physical characteristics such as thermal
resistance, chemical resistance, flame resistance, non-toxicity,
and electrical insulation characteristics. Thus, polyarylene
sulfide (PAS) (or polythioether sulfone (PTES)) can be used in
computer accessories and auto accessories; as a coating for parts
that come into contact with corrosive chemicals; and as industrial
fibers having chemical resistance.
However, conventional methods for preparing polyarylene sulfide
(PAS), polythioether sulfone (PTES), or monomers thereof are
halogen-containing processes that, in principle, results in a low
yield and produces unrecyclable halogen-containing byproducts that
can cause environmental pollution.
SUMMARY
According to embodiments of the disclosure, the disclosure provides
a method for preparing a compound. The method includes the
following steps. A compound having a structure represented by
Formula (I) is reacted with a compound having a structure
represented by Formula (III) in the presence of a compound having a
structure represented by Formula (II), obtaining a compound having
a structure represented by Formula (IV)
##STR00002## wherein Ar.sup.1 is substituted or unsubstituted aryl
group; X is --O--, --S--, or --NH--; R.sup.1 is independently
hydrogen or C.sub.1-6 alkyl group; R.sup.2 is hydroxyl group,
C.sub.1-6 alkyl group, phenyl group, or tolyl group; and R.sup.3 is
independently C.sub.1-6 alkyl group, C.sub.5-8 cycloalkyl group, or
C.sub.2-6 alkoxyalkyl group.
According to embodiments of the disclosure, the disclosure also
provides a method for preparing a polymer. The method includes the
following steps. A compound having a structure represented by
Formula (I) is reacted with a compound having a structure
represented by Formula (III) in the presence of a compound having a
structure represented by Formula (II), obtaining a compound having
a structure represented by Formula (IV). The compound having the
structure represented by Formula (IV) is reacted with a compound
(A), obtaining a compound having the structure represented by
Formula (V). The compound (A) is nitric acid, sulfuric acid, acetic
acid, hydrogen peroxide, or a combination thereof. The compound
having the structure represented by Formula (V) is reacted with a
compound having a structure represented by Formula (VI), obtaining
a polymer having a repeat unit represented by Formula (VII)
##STR00003## wherein Ar.sup.1 is substituted or unsubstituted aryl
group; X is --O--, --S--, or --NH--; R.sup.1 is independently
hydrogen or C.sub.1-6 alkyl group; R.sup.2 is hydroxyl group,
C.sub.1-6 alkyl group, phenyl group, or tolyl group; R.sup.3 is
independently C.sub.1-6 alkyl group, C.sub.5-8 cycloalkyl group, or
C.sub.2-6 alkoxyalkyl group; R.sup.5 is hydroxyl group, C.sub.1-6
alkyl group, phenyl group, or tolyl group; and Ar.sup.2 is
substituted or unsubstituted aryl diradical.
A detailed description is given in the following embodiments with
reference to the accompanying drawings.
DETAILED DESCRIPTION
The disclosure provides a method for preparing a compound, wherein
the starting materials or catalysts of the method for preparing a
compound are halogen-free compounds. Thus, no halogen-containing
side product is formed. In addition, there is no halogen-containing
compound remained in the obtained result. The method for preparing
a compound of the disclosure does not include an additional step
for removing a halogen-containing side product or residual
halogen-containing compound, thereby reducing preparation cost and
increasing product yield. Thus, a halogen-free monomer, which can
be used in a subsequent polymerization, is obtained.
Furthermore, the disclosure also provides a method for preparing a
polymer (such as polyether sulfone (PES) or polythioether sulfone
(PTES). The starting materials of the method for preparing the
monomer of the polymer and the method for preparing a polymer are
halogen-free compounds. Thus, no halogen-containing side product is
formed. In addition, there is no halogen-containing compound
remained in the obtained result. The method for preparing a polymer
of the disclosure does not include an additional step for removing
a halogen-containing side product or residual halogen-containing
compound, thereby reducing preparation cost and increasing product
yield. Thus, a halogen-free polymer is obtained. Furthermore, the
method for preparing a polymer of the disclosure includes
subjecting a monomer to an electrophilic polymerization and then
performing an oxidation after polymerization. Therefore, the
obtained polymer has an increased molecular weight and a reduced
polydispersity index (PDI).
According to embodiments of the disclosure, the disclosure provides
a method for preparing a compound, wherein the compound can serve
as a monomer for a subsequent polymerization (such as polyether
sulfone (PES) polymerization or polythioether sulfone (PTES)
polymerization). The method for preparing a compound includes:
reacting a compound having a structure represented by Formula (I)
with a compound having a structure represented by Formula (III) in
the presence of a compound having a structure represented by
Formula (II), obtaining a compound having a structure represented
by Formula (IV)
##STR00004## wherein Ar.sup.1 can be substituted or unsubstituted
aryl group; X can be --O--, --S--, or --NH--; R.sup.1 can be
independently hydrogen or C.sub.1-6 alkyl group; R.sup.2 can be
hydroxyl group, C.sub.1-6 alkyl group, phenyl group, or tolyl
group; and R.sup.3 can be independently C.sub.1-6 alkyl group,
C.sub.5-8 cycloalkyl group, or C.sub.2-6 alkoxyalkyl group. Herein,
the substituted aryl group of the disclosure means that at least
one hydrogen atom bonded to carbon atoms of the aryl group can be
replaced with C.sub.1-6 alkyl group.
According to embodiments of the disclosure, wherein Ar.sup.1 can be
substituted or unsubstituted phenyl group, biphenyl group, naphthyl
group, thienyl group, indolyl group, phenanthrenyl group, indenyl
group, anthracenyl group, or fluorenylene group. In particular, the
substituted phenyl group, substituted biphenyl group, substituted
naphthyl group, substituted thienyl group, substituted indolyl
group, substituted phenanthrenyl group, substituted indenyl group,
substituted anthracenyl group, or substituted fluorenylene group
means that at least one hydrogen atom bonded to carbon atoms of the
aforementioned group can be replaced with C.sub.1-6 alkyl
group.
According to embodiments of the disclosure, C.sub.1-6 alkyl group
can be linear or branched alkyl group, such as methyl group, ethyl
group, propyl group, isopropyl group, n-butyl group, t-butyl group,
sec-butyl group, isobutyl group, pentyl group, or hexyl group.
According to embodiments of the disclosure, R.sup.1 can be
independently hydrogen, methyl group, ethyl group, propyl group,
isopropyl group, n-butyl group, t-butyl group, sec-butyl group,
isobutyl group, pentyl group, or hexyl group.
According to embodiments of the disclosure, R.sup.2 can be hydroxyl
group, methyl group, ethyl group, propyl group, isopropyl group,
n-butyl group, t-butyl group, sec-butyl group, isobutyl group,
pentyl group, hexyl group, phenyl group, or tolyl group.
According to embodiments of the disclosure, R.sup.3 can be
independently methyl group, ethyl group, propyl group, isopropyl
group, n-butyl group, t-butyl group, sec-butyl group, isobutyl
group, pentyl group, hexyl group, cyclopentyl group, cyclohexyl
group, cycloheptyl group, cyclooctyl group, or
##STR00005## wherein 1.ltoreq.n.ltoreq.5, 0.ltoreq.m.ltoreq.4, and
1.ltoreq.n+m.ltoreq.5.
According to embodiments of the disclosure, The compound having the
structure of Formula (I) can be
##STR00006## ##STR00007## wherein R.sup.1 has the same definition
as above; and R.sup.4 can be independently hydrogen or C.sub.1-6
alkyl group.
According to embodiments of the disclosure, R.sup.4 can be
independently hydrogen, methyl group, ethyl group, propyl group,
isopropyl group, n-butyl group, t-butyl group, sec-butyl group,
isobutyl group, pentyl group, or hexyl group.
According to embodiments of the disclosure, the compound having the
structure of Formula (II) can be sulfuric acid, methanesulfonic
acid, benzenesulfonic acid, p-toluenesulfonic acid, or a
combination thereof.
According to embodiments of the disclosure, the compound having the
structure of Formula (III) can be
##STR00008##
According to embodiments of the disclosure, the disclosure provides
a method for preparing the compound having the structure of Formula
(IV), wherein the compound having the structure of Formula (IV) can
be
##STR00009## wherein R.sup.1, R.sup.3, and R.sup.4 have the same
definition as above.
According to embodiments of the disclosure, the method for
preparing the compound having the structure of Formula (IV) of the
disclosure can include dissolving the compound having the structure
of Formula (I) and the compound having the structure of Formula
(II) in a solvent, obtaining a mixture. Next, the compound having
the structure of Formula (III) is added into the mixture to undergo
a reaction, obtaining a compound having a structure represented by
Formula (IV). The synthesis pathway of the above reaction is as
follows:
##STR00010## wherein Ar.sup.1, X, R.sup.1, R.sup.2, and R.sup.3
have the same definition as above. Herein, the solvent can be any
solvent (such as halogen-free organic solvent) which can be used to
dissolve the compound having the structure of Formula (I) and the
compound having the structure of Formula (II). Furthermore, a
halogen-containing organic solvent, which is easily removed after
the reaction is complete and would not be active in the desired
reaction, can also serve as the solvent of the above reaction.
According to embodiments of the disclosure, the solvent can be an
aprotic solvent. The solvent, for example, can include
acetonitrile, linear or cyclic alkane (such as propane, butane, or
cyclohexane), haloalkane (dichloromethane, trichloromethane, or
dichloroethane). Furthermore, the reaction can be performed in the
absence of a solvent.
According to embodiments of the disclosure, in the method for
preparing the compound of the disclosure, the molar ratio of the
compound having the structure of Formula (II) to the compound
having the structure of Formula (I) can be from about 0.5 to 5;
Furthermore, in the method for preparing the compound of the
disclosure, The molar ratio of the compound having the structure of
Formula (I) to the compound having the structure of Formula (III)
can be from about 1 to 20, such as from about 1 to 3, or from about
1 to 10.
According to some embodiments of the disclosure, the method for
preparing the compound of the disclosure, after preparing the
compound having the structure of Formula (IV), further includes
reacting the compound having the structure represented by Formula
(IV) with a compound (A), obtaining a compound having the structure
represented by Formula (V)
##STR00011## wherein the compound (A) can be nitric acid, sulfuric
acid, acetic acid, hydrogen peroxide, or a combination thereof; and
Ar.sup.1, X, and R.sup.3 has the same definition as above.
According to embodiments of the disclosure, the disclosure provides
a method for preparing the compound having the structure of Formula
(V), wherein the compound having the structure of Formula (V) can
be
##STR00012## wherein R.sup.1, R.sup.3, and R.sup.4 have the same
definition as above.
According to embodiments of the disclosure, the method for
preparing the compound having the structure of Formula (V) of the
disclosure can include dissolving the compound having the structure
of Formula (I) and the compound having the structure of Formula
(II) in a first solvent, obtaining a mixture. Next, the compound
having the structure of Formula (III) is added into the mixture to
undergo a reaction, obtaining a compound having a structure
represented by Formula (IV). Next, the compound having the
structure of Formula (IV) is dissolved in a second solvent, and the
compound (A) is added to undergo a reaction, obtaining a compound
having the structure represented by Formula (V). The synthesis
pathway of the above reaction is as follows:
##STR00013## wherein Ar.sup.1, X, R.sup.1, R.sup.2 and R.sup.3 have
the same definition as above. Herein, when X is S, the S atom
bonded to R.sup.3 group can be selectively oxidized in comparison
with X since the S atom bonded to R.sup.3 group exhibits a
relatively low steric hindrance and has a suitable oxidation
potential for oxidation.
According to embodiments of the disclosure, the first solvent can
be any solvent which can be used to dissolve the compound having
the structure of Formula (I) and the compound having the structure
of Formula (II). The second solvent can be any solvent which can be
used to dissolve the compound having the structure of Formula (IV).
According to embodiments of the disclosure, a halogen-free organic
solvent can serve as the first solvent or the second solvent.
Furthermore, a halogen-containing organic solvent, which is easily
removed after the reaction is complete and would not be active in
the desired reaction, can also serve as the solvent of the above
reaction. According to embodiments of the disclosure, the first
solvent or the second solvent can be an aprotic solvent. The
solvent, for example, can include acetonitrile, linear or cyclic
alkane (such as propane, butane, or cyclohexane), or haloalkane
(dichloromethane, trichloromethane, or dichloroethane).
Furthermore, the reaction can be performed in the absence of a
solvent. The molar ratio of the compound having the structure of
Formula (IV) to the compound (A) can be from about 0.8 to 30.
According to embodiments of the disclosure, the disclosure provides
a method for preparing a polymer. The method for preparing a
polymer includes the following steps. First, a compound having a
structure represented by Formula (I) is reacted with a compound
having a structure represented by Formula (III) in the presence of
a compound having a structure represented by Formula (II),
obtaining a compound having a structure represented by Formula
(IV). Next, the compound having the structure represented by
Formula (IV) is reacted with a compound (A), obtaining a compound
having the structure represented by Formula (V), wherein the
compound (A) is nitric acid, sulfuric acid, acetic acid, hydrogen
peroxide, or a combination thereof. Next, the compound having the
structure represented by Formula (V) is reacted with a compound
having a structure represented by Formula (VI), obtaining a polymer
having a repeat unit represented by Formula (VII)
##STR00014## wherein Ar.sup.1, X, R.sup.1, R.sup.2, and R.sup.3 has
the same definition as above; R.sup.5 is hydroxyl group, C.sub.1-6
alkyl group, phenyl group, or tolyl group; and Ar.sup.2 is
substituted or unsubstituted aryl diradical. The method for
preparing a polymer of the disclosure can be used to prepare a
polymer having a number average molecular weight greater than or
equal to 1,000. It should be noted that the method for preparing a
polymer of the disclosure is particularly suitable for preparing a
polymer having a great number average molecular weight (such as
greater than or equal to 80,000) and a narrow polydispersity index
(PDI) (such as less than or equal to 2). According to embodiments
of the disclosure, the method for preparing a polymer of the
disclosure is particularly suitable for preparing a polymer having
a number average molecular weight from 80,000 to 500,000 and a
polydispersity index (PDI) from 1 to 2. According to some
embodiments of the disclosure, the method for preparing a polymer
of the disclosure is particularly suitable for preparing a polymer
having a number average molecular weight from 80,000 to 200,000 and
polydispersity index (PDI) from 1.4 to 2.
According to embodiments of the disclosure, R.sup.5 can be
hydroxyl, methyl group, ethyl group, propyl group, isopropyl group,
n-butyl group, t-butyl group, sec-butyl group, isobutyl group,
pentyl group, hexyl group, phenyl group, or tolyl group.
According to embodiments of the disclosure, the substituted aryl
diradical of the disclosure means that at least one hydrogen atom
bonded to carbon atoms of the aryl diradical can be replaced with
C.sub.1-6 alkyl group.
According to embodiments of the disclosure, Ar.sup.2 can be
substituted or unsubstituted phenylene group, biphenylene group,
naphthylene group, thienylene group, indolylene group,
phenanthrenylene group, indenylene group, anthracenylene group, or
fluorenylene group. In particular, the substituted phenylene group,
substituted biphenylene group, substituted naphthylene group,
substituted thienylene group, substituted indolylene group,
substituted phenanthrenylene group, substituted indenylene group,
substituted anthracenylene group, or substituted fluorenylene group
means that at least one hydrogen atom bonded to carbon atoms of the
aforementioned group can be replaced with C.sub.1-6 alkyl
group.
According to embodiments of the disclosure, in the method for
preparing the polymer of the disclosure, the molar ratio of the
compound having the structure of Formula (II) to the compound
having the structure of Formula (I) can be from about 0.5 to 5.
Furthermore, in the method for preparing the compound of the
disclosure, the molar ratio of the compound having the structure of
Formula (I) to the compound having the structure of Formula (III)
can be from about 1 to 20, such as from about 1 to 3, or from about
1 to 10. The molar ratio of the compound having the structure of
Formula (IV) to the compound (A) (such as nitric acid, sulfuric
acid, acetic acid, hydrogen peroxide, or a combination thereof) can
be from about 0.8 to 30; and the molar ratio of the compound having
the structure of Formula (V) to the compound having the structure
of Formula (VI) can be from about 0.8 to 20, such as from about 1.2
to 5. Furthermore, the compound having the structure of Formula
(VI) can serve as a reactant for reacting with the compound having
the structure of Formula (V), and the excessive compound having the
structure of Formula (VI) can also serve as the reaction
solvent.
According to embodiments of the disclosure, the compound having the
structure of Formula (VI) can be sulfuric acid, methanesulfonic
acid, benzenesulfonic acid, p-toluenesulfonic acid,
trifluoromethanesulfonic acid or a combination thereof.
Furthermore, according to embodiments of the disclosure, the
compound having the structure of Formula (II) and the compound
having the structure of Formula (VI) can be the same or
different.
According to embodiments of the disclosure, the method for
preparing the polymer of the disclosure can be used to prepare the
polymer having a repeat unit represented by Formula (VII). For
example, the repeat unit represented by Formula (VII) can be
##STR00015## wherein R.sup.1, R.sup.3, R.sup.4, and R.sup.5 have
the same definition as above.
According to embodiments of the disclosure, the method for
preparing the polymer having a repeat unit represented by Formula
(VII) of the disclosure can include dissolving the compound having
the structure of Formula (I) and the compound having the structure
of Formula (II) in a first solvent, obtaining a mixture. Next, the
compound having the structure of Formula (III) is added into the
mixture to undergo a reaction, obtaining a compound having a
structure represented by Formula (IV). Next, the compound having
the structure of Formula (IV) is dissolved in a second solvent, the
compound (A) is added to undergo a reaction, obtaining a compound
having the structure represented by Formula (V). Next, the compound
having the structure represented by Formula (V) is reacted with a
compound having a structure represented by Formula (VI), obtaining
a polymer having a repeat unit represented by Formula (VII). The
synthesis pathway for preparing the above polymer is as
follows:
##STR00016## polymer having a repeat unit represented by Formula
(VII)
##STR00017## wherein Ar.sup.1, Ar.sup.2, X, R.sup.1, R.sup.2,
R.sup.3, and R.sup.5 have the same definition as above.
According to embodiments of the disclosure, after preparing the
polymer having the repeat unit represented by Formula (VII), the
method for preparing the polymer of the disclosure further includes
reacting a nucleophile with the polymer having the repeat unit
represented by Formula (VII), obtaining a polymer having a repeat
unit represented by Formula (VIII)
##STR00018## wherein Ar.sup.2, X, R.sup.1, R.sup.3, and R.sup.5
have the same definition as above. The synthesis pathway of the
above method for preparing the polymer having the repeat unit
represented by Formula (VIII) is as follows:
##STR00019## polymer baying a repeat unit represented by Formula
(VII)
##STR00020## polymer having a repeat unit represented by Formula
(VIII)
##STR00021## wherein Ar.sup.1, Ar.sup.2, X, R.sup.1, R.sup.2,
R.sup.3 and R.sup.5 have the same definition as above.
According to embodiments of the disclosure, the nucleophile can be
substituted or unsubstituted pyridine or derivatives thereof (such
as pyridine or 4-methylpyridine), amine (such as triethylamine),
halogenated salt (such as potassium chloride), alcohol (such as
methanol or ethanol), amide (such as dimethylformamide,
dimethylacetamide, or N-methylpyrrolidone), or a combination
thereof. The equivalent ratio of the nucleophile to the moiety
represented by
##STR00022## of the polymer having the repeat unit represented by
Formula (VII) can be from 1 to 10. According to embodiments of the
disclosure, the nucleophile and the polymer having the repeat unit
represented by Formula (VII) can optionally be dissolved into an
organic solvent before undergoing the reaction.
According to embodiments of the disclosure, when X of the repeat
unit represented by Formula (VIII) is --O-- or --NH-- (i.e. the
repeat unit represented by Formula (VIII) is
##STR00023## wherein Ar.sup.2, and R.sup.1 have the same definition
as above), the method for preparing the polymer of the disclosure
can further include, after obtaining the polymer having the repeat
unit represented by Formula (VIII), reacting the polymer having the
repeat unit represented by Formula (VIII) with hydrogen peroxide
(H.sub.2O.sub.2), obtaining a polymer having a repeat unit
represented by Formula (X). Alternatively, the polymer having the
repeat unit represented by Formula (VIII) can be reacted with
hydrogen peroxide in the presence of the compound having a
structure represented by Formula (IX), obtaining the polymer having
the repeat unit represented by Formula (X)
##STR00024## wherein X can be --O-- or --NH--; R.sup.6 is C.sub.1-6
alkyl group; and Ar.sup.2 and R.sup.1 have the same definition as
above. The synthesis pathway of the above method for preparing the
polymer having the repeat unit represented by Formula (X) is as
follows:
##STR00025## polymer having a repeat unit represented by Formula
(VII)
##STR00026## polymer having a repeat unit represented by Formula
(VIII)
##STR00027## polymer having a repeat unit represented by Formula
(X)
##STR00028## wherein X can be --O-- or --NH--; and Ar.sup.1,
Ar.sup.2, R.sup.1, R.sup.2, R.sup.3, R.sup.5 and R.sup.6 have the
same definition as above.
According to other embodiments of the disclosure, in the method for
preparing the polymer having the repeat unit represented by Formula
(X) of the disclosure, the polymer having the repeat unit
represented by Formula (VIII), the compound having the structure of
Formula (IX), and hydrogen peroxide can be dissolved into a solvent
before undergoing the reaction. For example, the solvent can be
amide-type solvent or sulfoxide-type solvent.
According to embodiments of the disclosure, R.sup.6 can be
independently methyl group, ethyl group, propyl group, isopropyl
group, n-butyl group, t-butyl group, sec-butyl group, isobutyl
group, pentyl group, or hexyl group.
According to embodiments of the disclosure, when X of the repeat
unit represented by Formula (VII) is --S-- (i.e. the repeat unit
represented by Formula (VII) is
##STR00029## wherein Ar.sup.2, R.sup.1, R.sup.3, and R.sup.5 have
the same definition as above), the method for preparing the polymer
of the disclosure, after obtaining the polymer having the repeat
unit represented by Formula (VII), can further include reacting the
polymer having the repeat unit represented by Formula (VII) with
hydrogen peroxide, obtaining a polymer having a repeat unit
represented by Formula (XI). Alternatively, the polymer having the
repeat unit represented by Formula (VII) is reacted with hydrogen
peroxide in the presence of the compound having the structure of
Formula (IX), obtaining the polymer having the repeat unit
represented by Formula (XI).
##STR00030## wherein X can be --S--; and Ar.sup.2, R.sup.1,
R.sup.3, R.sup.5 and R.sup.6 have the same definition as above. The
synthesis pathway of the above method for preparing the polymer
having the repeat unit represented by Formula (XI) is as
follows:
##STR00031## polymer having a repeat unit represented by Formula
(VII)
##STR00032## polymer having a repeat unit represented by Formula
(XI)
##STR00033## wherein X can be --S--; and Ar.sup.1, Ar.sup.2,
R.sup.1, R.sup.2, R.sup.3, R.sup.5 and R.sup.6 have the same
definition as above.
According to other embodiments of the disclosure, in the method for
preparing the polymer having a repeat unit represented by Formula
(XI) of the disclosure, the polymer having the repeat unit
represented by Formula (VII) and hydrogen peroxide can be dissolved
into an organic solvent and then the mixture is reacted with the
compound having the structure represented by Formula (IX) to
undergo the reaction. For example, the solvent can be nitrile-type
solvent, amide-type solvent, or sulfoxide-type solvent.
Furthermore, the polymer having the repeat unit represented by
Formula (VII), the compound having the structure represented by
Formula (IX), and hydrogen peroxide can be dissolved into an
organic solvent before undergoing the reaction.
According to embodiments of the disclosure, after preparing the
polymer having a repeat unit represented by Formula (XI), the
method for preparing the polymer of the disclosure can further
include reacting a nucleophile with the polymer having the repeat
unit represented by Formula (XI), obtaining a polymer having a
repeat unit represented by Formula (XII)
##STR00034## wherein Ar.sup.2, R.sup.1, R.sup.3, and R.sup.5 have
the same definition as above. The synthesis pathway of the above
method for preparing the polymer having the repeat unit represented
by Formula (XII) is as follows:
##STR00035## polymer having a repeat unit represented by Formula
(VII)
##STR00036## polymer having a repeat unit represented by Formula
(XI)
##STR00037## polymer having a repeat unit represented by Formula
(XII)
##STR00038## wherein X is --S--; and Ar.sup.1, Ar.sup.2, R.sup.1,
R.sup.2, R.sup.3, R.sup.5, and R.sup.6 have the same definition as
above.
According to embodiments of the disclosure, the nucleophile can be
substituted or unsubstituted pyridine or derivatives thereof (such
as pyridine or 4-methylpyridine), amine (such as triethylamine),
halogenated salt (such as potassium chloride), alcohol (such as
methanol or ethanol), amide (such as dimethylformamide,
dimethylacetamide, or N-methylpyrrolidone), or a combination
thereof. The equivalent ratio of the nucleophile to the moiety
represented by
##STR00039## of the polymer having the repeat unit represented by
Formula (XI) can be from 1 to 10. According to embodiments of the
disclosure, the nucleophile and the polymer having the repeat unit
represented by Formula (XI) can optionally be dissolved into an
organic solvent before undergoing the reaction.
Below, exemplary embodiments will be described in detail so as to
be easily realized by a person having ordinary knowledge in the
art. The inventive concept may be embodied in various forms without
being limited to the exemplary embodiments set forth herein.
Descriptions of well-known parts are omitted for clarity.
Example 1
5 g of diphenyl ether, 11.7 g of benzenesulfonic acid, and 50 ml of
dichloromethane were added into a reaction bottle under nitrogen
atmosphere, and then cooled to 15.degree. C. Next, 5.54 g of
1,2-dimethyldisulfane was added into the reaction bottle. After
reacting at 15.degree. C. for 20 hr, the result was mixed with 50
ml of sodium hydroxide aqueous solution (the weight ratio of sodium
hydroxide to water is 1:10). After stirring for 0.5 hr, the result
was extracted three times using dichloromethane and water as the
extraction solvent. Next, an organic phase was separated and dried,
obtaining Compound (1). The synthesis pathway of the above reaction
was as follows:
##STR00040##
Compound (1) was analyzed by nuclear magnetic resonance (NMR)
spectroscopy and the result is as follows: .sup.1H NMR (400 MHz,
ppm, CDCl.sub.3): 2.50 (--CH.sub.3, 3H, s), 7.00 (phenyl, 4H, m),
7.14 (phenyl, 1H, t), 7.32-7.41 (phenyl, 4H, m).
Example 2
0.73 g of Compound (1), 12 ml of nitric acid aqueous solution (with
a concentration of 20%), and 4 ml of acetonitrile were added into a
reaction bottle. After stirring at room temperature for 4 hr, 10 ml
of sodium hydroxide aqueous solution (with a concentration of 3%)
was added into the reaction bottle. Next, after the reaction was
complete, the result was separated and dried, obtaining Compound
(2) (orange powder). The synthesis pathway of the above reaction
was as follows:
##STR00041##
Compound (2) was analyzed by nuclear magnetic resonance (NMR)
spectroscopy and the result is as follows: .sup.1H NMR (400 MHz,
ppm, CD.sub.3CO): 2.71 (--CH.sub.3, 3H, s), 7.10-7.25 (phenyl, 5H,
m), 7.44-7.48 (phenyl, 2H, t), 7.70-7.72 (phenyl, 2H, d).
Example 3
0.65 g of Compound (2) was added into a reaction bottle. Next, 3 ml
of methanesulfonic acid (CH.sub.3SO.sub.3H) was added into the
reaction bottle placed in an ice bath. After reacting for 1 hr, the
reaction bottle was raised to room temperature and then reacted at
room temperature for 20 hr, obtaining a solution including Polymer
(1). Next, the solution including Polymer (1) was added into 100 ml
of ethyl ether and stirred for 30 min. Next, 6 ml of
4-methylpyridine was added under nitrogen atmosphere and then the
result was stirred at 100.degree. C. for 4-6 hr. After the reaction
was complete, the result was added into 100 ml of hydrochloric acid
solution (with a concentration of 10%) and then stirred for 10 min.
After concentrating, Polymer (2) was obtained. The synthesis
pathway of the above reaction was as follows:
##STR00042##
Polymer (2) was analyzed by nuclear magnetic resonance (NMR)
spectroscopy and the result is as follows: .sup.1H NMR (400 MHz,
ppm, (CD.sub.3).sub.2SO): 7.04 (phenyl, d), 7.36 (phenyl, d).
Example 4
0.2 g of Polymer (2), 10 ml of acetic acid, 0.9 g of hydrogen
peroxide solution (with a concentration of 30%) and 2 ml of
dimethylacetamide (DMAc) were added into a reaction bottle, and the
reaction bottle was stirred at 80.degree. C. for 6 hr. Next, the
result was concentrated, obtaining Polymer (3). The synthesis
pathway of the above reaction was as follows:
##STR00043##
Polymer (3) was analyzed by nuclear magnetic resonance (NMR)
spectroscopy and the result is as follows: .sup.1H NMR (400 MHz,
ppm, (CD.sub.3).sub.2SO): 7.28 (phenyl, d), 7.99 (phenyl, d). Next,
Polymer (3) was analyzed by Fourier-transform infrared (FT-IR)
spectroscopy, and the result shows that the strong absorption peaks
are 1483 cm.sup.-1 (characteristic vibration frequency of benzene
ring), 1575 cm.sup.-1 (characteristic vibration frequency of
benzene ring), 1295 cm.sup.-1 (asymmetry vibration frequency of
S.dbd.O), 1318 cm.sup.-1 (asymmetry vibration frequency of
S.dbd.O), and 1145 cm.sup.-1 (symmetry vibration frequency of
S.dbd.O). The properties of Polymer (3) were measured by a
differential scanning calorimetry (DSC), and the result shows
Polymer (3) has a glass transition temperature (Tg) of about
210.degree. C. Polymer (3) was analyzed by gel permeation
chromatography (GPC), and the results show Polymer (3) has a weight
average molecular weight (Mw) of about 128,287, a number average
molecular weight (Mn) of about 85,435, and a polydispersity index
(PDI) of about 1.5.
Example 5
5.58 g of diphenyl sulfide and 5.64 g of 1,2-dimethyldisulfane were
added into a reaction bottle, and then 50 ml of dichloromethane as
solvent was added into the reaction bottle. Next, 11.7 g of
benzenesulfonic acid was added into the reaction bottle. After
reacting at 15.degree. C. for 44 hr, the result was extracted three
times using 150 ml of n-hexane dichloromethane and water as the
extraction solvent. Next, an organic phase was separated, dried,
and purified by column chromatography, obtaining Compound (3). The
synthesis pathway of the above reaction was as follows:
##STR00044##
Compound (3) was analyzed by nuclear magnetic resonance (NMR)
spectroscopy and the result is as follows: .sup.1H NMR (400 MHz,
ppm, CDCl.sub.3): 2.50 (--CH.sub.3, 3H, s), 7.21-7.34 (phenyl, 9H,
m).
Example 6
5.07 g of Compound (3) was added into a reaction bottle, and then
20 ml of acetonitrile as solvent was added into the reaction
bottle. Next, 60 ml of nitric acid aqueous solution (with a
concentration of 20%) was added into the reaction bottle. After
reacting at room temperature for 4 hr, 12 g of sodium hydroxide was
added into the reaction bottle to neutralize the solution. The
result was extracted three times using 150 ml of dichloromethane as
the extraction solvent. Next, an organic phase was separated and
dried, obtaining Compound (4). The synthesis pathway of the above
reaction was as follows:
##STR00045##
Compound (4) was analyzed by nuclear magnetic resonance (NMR)
spectroscopy and the result is as follows: .sup.1H NMR (400 MHz,
ppm, CDCl.sub.3): 2.73 (--CH.sub.3, 3H, s), 7.34-7.49 (phenyl, 9H,
m).
Example 7
3 g of Compound (4) was added into a reaction bottle, and 10 ml of
methanesulfonic acid was added into the reaction bottle at
15.degree. C. After reacting for 20 hr, 50 ml of water was added
into the reaction bottle to cause a precipitation. The precipitate
was separated and dried, obtaining a white solid. The white solid
was dissolved in a solvent including 46 ml of chloroform and 46 ml
of trifluoroacetic acid. Next, 4.14 g of hydrogen peroxide aqueous
solution (with a concentration of 30%) was added and then the
result was reacted at 60.degree. C. for 5 hr. After the reaction
was complete, the result was mixed with a water to cause a
precipitation. The precipitate was separated and dried, obtaining
Polymer (4). The synthesis pathway of the above reaction was as
follows:
##STR00046##
Polymer (4) was analyzed by nuclear magnetic resonance (NMR)
spectroscopy and the result is as follows: .sup.1H NMR (400 MHz,
ppm, d.sup.6-DMSO): 7.56 (phenyl, 4H, s), 7.93 (phenyl, 4H, s). The
properties of Polymer (4) were measured by a differential scanning
calorimetry (DSC), and the result shows Polymer (4) has a glass
transition temperature (Tg) of about 222.degree. C.
Accordingly, the disclosure provides a method for preparing a
compound, wherein the starting material or catalyst of the method
for preparing a compound is a halogen-free compound. Thus, no
halogen-containing side product is formed. In addition, there is no
halogen-containing compound remained in the obtained result. The
method for preparing a compound of the disclosure does not include
an additional step for removing a halogen-containing side product
or residual halogen-containing compound, thereby reducing
preparation cost and increasing product yield. Thus, a halogen-free
monomer, which can be used in a subsequent polymerization, is
obtained. Furthermore, the disclosure also provides a method for
preparing a polymer (such as polyether sulfone (PES) or
polythioether sulfone (PTES)). Since the method for preparing a
polymer includes subjecting a monomer to an electrophilic
polymerization in an acidic environment and then performing an
oxidation after polymerization, the obtained polymer exhibits
increased molecular weight and relatively low polydispersity index
(PDI).
It will be clear that various modifications and variations can be
made to the disclosed methods and materials. It is intended that
the specification and examples be considered as exemplary only,
with the true scope of the disclosure being indicated by the
following claims and their equivalents.
* * * * *